1-isonicotinyl-2-alkenyl-2-alkyl-hydrazine



United States Patent I-ISONICOTINYL-Z-ALKENYL-2-ALKYL- HYDRAZINE Herman Herbert Fox, Passaic, N. J., assignor to Hoffmann-La Roche Inc., Roche Park, Nutley, N. J., a cor- I v poration of New Jersey No Drawing; Application June 1, 1954, Serial No. 433,843

6 Claims. (Cl. 260-295) resents a lower alkenyl radical.

Illustrative values of R include methyl, ethyl, propyl and the like. Illustrative values of R include vinyl,

allyl, crotyl and the like. Compounds of the above formula are bases, and are capable of forming acid addition salts with organic and inorganic acids, e. g. hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, tartaric acid, .ethanesulfonic acid, oxalic acid and the like. Accordingly, the invention also includes acid addition salts of bases having the above general formula. A particularly preferred class of acid addition salts are those formed by bases of theabove formula with the relatively non-toxic acids ordinarily employed in making pharmaceutically useful materials, such as hydrochloric acid, hydrobromic acid, tartaric acid, citric acid and the like. invention are useful as antituberculous agents.

A general process for preparing the compounds of the invention comprises reacting a l-isonicotinyl-Z-lower alkyl hydrazine with a lower alkenyl halide, preferably a chloride or a bromide, and preferably in the presenceof an acid binding agent. An alternative process for preparing the compounds of the invention comprises reacting an isonicotinic acid halide, e. g. isonicotinyl chloride or isonicotinyl bromide, or an acid addition salt of an isonicotinic acid halide, with a l-lower alkenyl-l-lower alkylhydrazine, preferably in the presence of an acid binding agent.

The invention is further disclosed in the following examples, which are illustrative but not limitative thereof:

Example 1 To a solution of 2.3 g. of sodium in 100 cc. of ethanol was added, with stirring, 15 g. of l-isonicotinyl-Z-methylhydrazine. When solution was complete, 8.5 cc. of allyl chloride was added with stirring and the mixture was refluxed for about 30 minutes. The reaction mixture was then filtered to remove the precipitated sodium chloride and the clear filtrate was evaporated under vacuum to leave an'oil comprising l-isonicotinyl-Z-allyl-Z-methylhy- The compounds of the I 2-allyl-2-isopropylhydrazine dihydrochloride.

2,744,113 Patented May 1, 1956 drazine. On treatment with ethanolic hydrogen chloride, the oil gave a crystalline precipitate of 1-isonicotinyl-2- al1yl-2-methylhydrazine dihydrochloride. Upon recrystallization from isopropanol, the pure product was obtained in the form of white crystals which melted with decompo sition at 162.5-163.5 C., corrected.

7 Example 2 To a solution of 2.3 g. of sodium in cc. of ethanol was added with stirring 16.5 g. of l-isonicotinyl-Z-ethylhydrazine. When solution was complete, 8.5 cc. of allyl chloride was added with stirring and the resulting mixture was refluxed for about 20 minutes. The reaction mix Example 3 17.9 grams of 1-isonieotinyl-2-isopropylhydrazine were dissolved in a, solution containing 2.3 grams of sodium metal in 100 cc. of absolute ethanol. 9 grams of allyl chloride were added to the solution and the mixture was refluxed for about 10 minutes. The reaction mixture was cooled, the sodium chloride which had formed was filtered off, and the ethanol was removed under vacuum. The

oily residue comprising l-isonicotinyl-2-allyl-2-isopropylhydrazine was dissolved in isopropanol, and an excess of ethanolic hydrogen chloride was added to the solution. The mixture was heated to boiling and then cooled with vigorous scratching to give a precipitate of l-isonicotinyl- Upon recrystallization from ethanol, the pure product was obtained in the form ofwhite needles which melted with decomposition at 188.5-189.5 C.

The same compound was also obtained when 0.69 gram of lithium metal was employed in the place of the sodium metal.

This application is a continuation-in-part of my application Serial No. 275,250, filed March 7, 1952.,

I claim: 7

,1. A compound selected from the class consisting of l-isonicotinyl-Z-lower alkenyl-Z-lower alkylhydrazine and acid addition salts thereof.

2. 1-isonicotinyl-2-allyl-2-methylhydrazine.

3.1-isoriicotinyl-2-allyl-2-ethylhydrazine. I

4. l-isonicotinyl-2-allyl-2-isopropylhydrazine.

5. An acid addition salt of l-isonicotinyl-Z-lower alkenyl-Z-lower alkylhydrazine.

6. l-isonicbtinyl-Z-lower alkenyl-Z-lower alkylhydrazine. 

1. A COMPOUND SELECTED FROM THE CLASS CONSISTING OF 1-ISONICOTINYL-2-LOWER ALKENYL-2-LOWER ALKYLHYDRAZINE AND ACID ADDITION SALTS THEREOF. 